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Journal of Colloid and Interface Science 283 (2005) 446–451

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Preparation and adsorption properties of monodisperse chitosan-bound


Fe3O4 magnetic nanoparticles for removal of Cu(II) ions
Yang-Chuang Chang, Dong-Hwang Chen ∗
Department of Chemical Engineering, National Cheng Kung University, Tainan, Taiwan 701, Republic of China
Received 13 July 2004; accepted 9 September 2004

Abstract
Monodisperse chitosan-bound Fe3 O4 nanoparticles were developed as a novel magnetic nano-adsorbent for the removal of heavy metal
ions. Chitosan was first carboxymethylated and then covalently bound on the surface of Fe3 O4 nanoparticles via carbodiimide activation.
Transmission electron microscopy micrographs showed that the chitosan-bound Fe3 O4 nanoparticles were monodisperse and had a mean
diameter of 13.5 nm. X-ray diffraction patterns indicated that the magnetic nanoparticles were pure Fe3 O4 with a spinel structure, and the
binding of chitosan did not result in a phase change. The binding of chitosan was also demonstrated by the measurement of zeta potential,
and the weight percentage of chitosan bound to Fe3 O4 nanoparticles was estimated to be about 4.92 wt%. The chitosan-bound Fe3 O4
nanoparticles were shown to be quite efficient for the removal of Cu(II) ions at pH > 2. In particular, the adsorption rate was so fast that
the equilibrium was achieved within 1 min due to the absence of internal diffusion resistance. The adsorption data obeyed the Langmuir
equation with a maximum adsorption capacity of 21.5 mg g−1 and a Langmuir adsorption equilibrium constant of 0.0165 L mg−1 . The pH
and temperature effects revealed that the adsorption capacity increased significantly with increasing pH at pH 2–5, and the adsorption process
was exothermic in nature with an enthalpy change of −6.14 kJ mol−1 at 300–330 K.
 2004 Elsevier Inc. All rights reserved.

Keywords: Chitosan; Magnetic; Nanoparticles; Adsorbent; Cu(II)

1. Introduction as ionic exchange groups. It was shown to be quite fast


and efficient for the adsorption of enzyme and basic dyes
Most of commercialized or developing adsorbents are due to high specific surface area and the absence of internal
submicrometer to micrometer sized and have large internal diffusion resistance [17–20]. Unfortunately, the PAA-based
porosities to ensure adequate surface area for adsorption. magnetic nano-adsorbent is less effective for the adsorption
However, the diffusion limitation within the particles leads of heavy metal ions.
to decreases in the adsorption rate and available capacity. Chitosan is a natural polysaccharide with many useful
Recently, the combination of organic and inorganic compo- features such as hydrophilicity, biocompatibility, biodegrad-
nents in a single particle at the nano-sized level has attracted ability, antibacterial properties, and remarkable affinity for
considerable attention because of the wide potential appli- many biomacromolecules. It and its derivatives have great
cations in many fields such as separation processes, opto- potential applications in the areas of biotechnology, bio-
electronics, catalysts and/or sensors, biotechnology, medical medicine, food ingredients, and cosmetics [21–27]. Note-
diagnosis, and therapy [1–16]. Therefore, we developed worthily, chitosan is also capable of adsorbing a number
a novel magnetic nano-adsorbent which using iron oxide of metal ions because its amino groups can serve as chela-
(Fe3 O4 ) nanoparticles as cores and polyacrylic acid (PAA) tion sites [28–30]. Thus, the binding of chitosan onto Fe3 O4
nanoparticles will probably yield another novel magnetic
* Corresponding author. Fax: +886-6-2344496. nano-adsorbent for the efficient removal of heavy metal
E-mail address: chendh@mail.ncku.edu.tw (D.-H. Chen). ions.
0021-9797/$ – see front matter  2004 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2004.09.010
Y.-C. Chang, D.-H. Chen / Journal of Colloid and Interface Science 283 (2005) 446–451 447

The preparations of chitosan-conjugated Fe3 O4 particles isopropanol) was added into the reaction mixture in drops
by a coprecipitation method, crosslinking method, and co- in 30 min. After reaction for 4 h at the same temperature,
valent binding method using coupling agents have been 200 ml of ethyl alcohol (70%) was added to stop the reac-
reported [31]. The resultant magnetic composites were ei- tion. Finally, the solid was filtered, rinsed with 70 and 99%
ther aggregated or unstable due to polymer crosslinking ethyl alcohol to desalt and dewater, and dried in an oven
or physisorption, the particle sizes were above 100 nm, at 50 ◦ C.
even larger than 1000 nm. So, following our previous work The binding of carboxymethyl chitosan was conducted
on PAA-bound magnetic nanoparticles, the preparation of following our previous work on the preparation of PAA-
monodisperse chitosan-bound Fe3 O4 nanoparticles was at- bound magnetic nanoparticles [17]. First, 100 mg of Fe3 O4
tempted in this study. Since chitosan has no suitable func- nanoparticles was added to 2 ml of buffer A (0.003 M phos-
tional groups to bind directly onto Fe3 O4 nanoparticles, it phate, pH 6, 0.1 M NaCl). Then, the reaction mixture was
was first carboxmethylated and then covalently bound onto sonicated for 10 min after adding 0.5 ml of carbodiimide
Fe3 O4 nanoparticles via carbodiimide activation. The sizes, solution (0.025 g ml−1 in buffer A). Finally, 2.5 ml of car-
structures, and surface charges of the product were charac- boxymethyl chitosan solution (50 mg ml−1 in buffer A) was
terized by transmission electron microscopy (TEM), X-ray added and the reaction mixture was sonicated for 60 min.
diffraction (XRD), and zeta potential meter. The capability The chitosan-bound Fe3 O4 nanoparticles were recovered
and behavior for the adsorption of heavy metal ions were in- from the reaction mixture by placing the bottle on a per-
vestigated using Cu(II) ions as a model compound. manent magnet with a surface magnetization of 6000 G.
The magnetic particles settled within 1–2 min and then were
washed with water and ethanol. NaCl was used for the
2. Materials and methods flocculation of magnetic nanoparticles. Its addition could
accelerate the magnetic separation, particularly in alkaline
2.1. Materials solutions [33].

Chitosan (low viscous), chloroacetic acid sodium salt, 2.3. Characterizations of chitosan-bound
o-phthaldialdehyde, β-mercaptoethanol, and ferrous chlo- Fe3 O4 nanoparticles
ride tetrahydrate were purchased from Fluka (Buchs). Car-
bodiimides (cyanamide, CH2 N2 ) were supplied from Sigma The amino groups on the chitosan-bound Fe3 O4 magnetic
Chemical Co. (St. Louis, MO). Ferric chloride, 6-hydrate nanoparticles were determined by spectrophotometric as-
was purchased from J.T. Baker (Phillipsburg). Glycine, say based on the reaction of o-phthaldialdehyde (OPA) and
natriumtetraborate-10-hydrate, and Cu(II) nitrate-2,5-hy- β-mercaptoethanol (BME) with primary amines [17,34].
drate were obtained from Riedel-deHaën (Seelze). Ammo- First, two reagents were freshly prepared as follows. For re-
nium hydroxide (29.6%) was supplied by TEDIA (Fairfield). action of primary amines of the solid, 300 µl ethanol solution
The water used throughout this work was the reagent-grade containing 0.25 M OPA and 300 µl of 0.1 M sodium borate
water produced by the Milli-Q SP ultrapure water purifica- (pH 9.5) containing 4% β-mercaptoethanol were added to
tion system of Nihon Millipore Ltd., Tokyo. All other chem- water to yield 50 ml of reagent 1 (R1). For the determina-
icals were the guaranteed or analytic grade reagents com- tion of excess OPA, 500 µl of 0.06 M glycine and 500 µl
mercially available and used without further purification. of 0.1 M sodium borate (pH 9.5) containing 0.5% BME
were added to water to yield 30 ml of reagent 2 (R2). Sec-
2.2. Preparation of chitosan-bound Fe3 O4 nanoparticles ondly, 20 mg of magnetic nanoparticles was incubated with
5 ml reagent R1 for 5 min at 25 ◦ C. The liquid solution
Fe3 O4 nanoparticles were prepared by coprecipitating was then separated from the magnetic nanoparticles via a
Fe2+ and Fe3+ ions by ammonia solution and treating un- permanent magnet. To 4 ml of 0.1 M sodium borate and
der hydrothermal conditions [17–20]. Ferric and ferrous 200 µl of reagent R2 in a test tube, 100 µl of supernatant
chlorides (molar ratio 2:1) were dissolved in water at a was added. After mixing by vortex for several minutes, the
concentration of 0.3 M iron ions. Chemical precipitation absorbance of the sample at 340 nm was determined on a
was achieved at 25 ◦ C under vigorous stirring by adding Hitachi U-3000 spectrophotometer. Finally, a reference so-
NH4 OH solution (29.6%). During the reaction process, the lution was prepared according to the above procedures but in
pH was maintained at about 10. The precipitates were heated the absence of magnetic nanoparticles. The concentration of
at 80 ◦ C for 30 min, washed several times with water and amino groups on the surface of magnetic nanoparticles was
ethanol, and then finally dried in a vacuum oven at 70 ◦ C. determined from the difference between the absorbances of
Chitosan was carboxymethylated according to the method reference solution and sample, using a molar absorption co-
of Chen and Park [32]. First, 3 g chitosan and 15 g sodium efficient ε = 6623 M−1 cm−1 obtained from the calibration
hydroxide were added into 100 ml of isopropanol/water curve.
(80/20) mixture at 60 ◦ C to swell and alkalize for 1 h. Then, The size and morphology of magnetic nanoparticles
20 ml of monochloroacetic acid solution (0.75 g ml−1 in were observed by TEM using a JEOL Model JEM-1200EX
448 Y.-C. Chang, D.-H. Chen / Journal of Colloid and Interface Science 283 (2005) 446–451

at 80 kV. The sample for TEM analysis was obtained


by placing a drop of the magnetic nanoparticle-dispersed
aqueous solution onto a Formvar-covered copper grid and
evaporated in air at room temperature. Before the sample
was withdrawn, the dispersed solution was sonicated for
1 min to obtain the better particle dispersion on the cop-
per grid. XRD measurement was performed on a Rigaku
D/max III. V X-ray diffractometer using CuKα radiation
(λ = 0.1542 nm). The zeta potentials of the naked and
chitosan-bound Fe3 O4 nanoparticles were measured on a
Malvern ZEN2600 Zetasizer Nano Z. Fig. 2. XRD patterns for the naked (a) and chitosan-bound (b) Fe3 O4 nano-
particles.

2.4. Adsorption studies


diameter of 13.5 nm. This reveals that the binding process
The adsorption of Cu(II) ions by the chitosan-bound did not significantly result in the agglomeration and the
Fe3 O4 magnetic nanoparticles (as a magnetic nano-adsor- change in size of the particles. This could be attributed to
bent) was investigated in aqueous solutions at pH 2–5 and the reaction occurring only on the particle surface, and thus
300–330 K. In general, 105.17 mg magnetic nano-adsorbent our attempt to prepare monodisperse chitosan-bound Fe3 O4
(i.e., 5.17 mg chitosan on 100 mg Fe3 O4 ) was added to nanoparticles in this work has been achieved.
5 ml of copper nitrate solution. After mixing by vortex for Fig. 2 shows the XRD patterns for the naked and
1 min, the magnetic nano-adsorbent was removed magnet- chitosan-bound Fe3 O4 nanoparticles. Six characteristic peaks
ically from the solution. The solution pH was adjusted by for Fe3 O4 (2θ = 30.1, 35.5, 43.1, 53.4, 57.0, and 62.6◦ ),
NaOH or HCl. The concentrations of Cu(II) ions were mea- marked by their indices ((220), (311), (400), (422), (511),
sured using a GBC Avanta atomic absorption spectrometer. and (440)), were observed for both samples. These peaks
The concentration of magnetic nano-adsorbent was fixed at are consistent with the database in JCPDS file (PCPDFWIN
21.034 mg ml−1 . Unless otherwise specified, the absorption v.2.02, PDF No. 85-1436) and reveal that the resultant
experiments were performed in aqueous solution at pH 5 nanoparticles were pure Fe3 O4 with a spinel structure. Also,
and 300 K. the binding process did not result in the phase change of
Fe3 O4 . It is explained that the binding process did not result
in the phase change of Fe3 O4 .
3. Results and discussion
3.2. Amount of chitosan bound on Fe3 O4 nanoparticles
3.1. Particle size and structure of chitosan-bound
Fe3 O4 nanoparticles According to the increased weight after chitosan binding,
the amount of chitosan bound on Fe3 O4 nanoparticles could
The typical TEM micrographs for the naked and chitosan- be estimated to be 5.25 mg per 100 mg Fe3 O4 . To further
bound Fe3 O4 nanoparticles are shown in Fig. 1. It was clear confirm this binding amount, the amino groups of chitosan
that both the naked and the chitosan-bound Fe3 O4 nanopar- on Fe3 O4 nanoparticles were quantified by the spectrophoto-
ticles were essentially monodisperse and had a similar mean metric assay based on the reaction of amino groups of solids
with an excess of OPA and subsequent quantitative deter-
mination of unreacted OPA by reaction with glycine. It was
found that about 0.0233 mmol of amino groups per 100 mg
Fe3 O4 nanoparticles was available. Accordingly, the quan-
tity of carboxymethyl chitosan on Fe3 O4 nanoparticles could
be estimated to be 5.08 mg per 100 mg Fe3 O4 . This was in
agreement with that obtained from weight difference. The
average value 5.17 mg (i.e., 4.92 wt%) was adopted in the
following investigations.

3.3. Zeta-potential analysis

The zeta potentials of the naked and chitosan-bound


Fe3 O4 nanoparticles (0.1 mg ml−1 ) were measured in 10−3 M
NaCl aqueous solutions at pH 2.5–9.5 (adjusted by NaOH
Fig. 1. TEM micrographs for the naked (a) and chitosan-bound (b) Fe3 O4 or HCl). As shown in Fig. 3, the isoelectric point (pI ) of the
nanoparticles. naked Fe3 O4 nanoparticles was about 6.7, consistent with
Y.-C. Chang, D.-H. Chen / Journal of Colloid and Interface Science 283 (2005) 446–451 449

Fig. 3. Zeta potentials of the naked (P) and chitosan-bound (!) Fe3 O4 Fig. 5. Effect of pH on the adsorption of Cu(II) ions by magnetic nano-
nanoparticles at different pH. adsorbent. Initial Cu(II) ion concentration: 200 (!) and 1150 mg L−1 (P).

Fig. 4. Dependence of adsorption capacity on contact time. Fig. 6. Equilibrium isotherm for the adsorption of Cu(II) ions on magnetic
nano-adsorbent at pH 5 and 300 K. The inset illustrates the linear depen-
dence of Ce /q on Ce .
the literature value of 6.5 [35]. After chitosan bonding, the
pI was shifted to 5.95. This also confirms the binding of
pH > 5, white Cu(OH)2 precipitate formed and so no ad-
chitosan and reveals that the chitosan-bound Fe3 O4 nanopar-
sorption experiments were performed. Noteworthly, almost
ticles were positively charged at pH < 5.95.
no Cu(II) ions were adsorbed at pH 2. This condition might
be utilized for the desorption of Cu(II) ions from the mag-
3.4. Adsorption properties netic nano-adsorbent.
The equilibrium isotherm for the adsorption of Cu(II)
The feasibility of chitosan-bound Fe3 O4 nanoparticles ions on magnetic nano-adsorbent at pH 5 and 300 K is shown
as a magnetic nano-adsorbent for the removal of heavy in Fig 6. The adsorption data were analyzed according to the
metal ions from aqueous solutions was demonstrated using linear form of the Langmuir isotherm as follow [36],
Cu(II) ions as a model compound. First, the time required
Ce 1 Ce
to achieve adsorption equilibrium was determined. The typ- = + , (1)
ical experiments were conducted at pH 5, 300 K, and an q Kqm qm
initial Cu(II) ion concentration of 1100 mg L−1 . As shown where q is the adsorption capacity (mg g−1 ) based on the
in Fig. 4, the adsorption capacities (q) for the contact time dry weight of nano-adsorbent, Ce is the equilibrium concen-
of 1 to 60 min had no significant differences. This reveals tration (mg L−1 ) in solution, qm is the maximum adsorption
that the adsorption equilibrium was reached within 1 min. capacity (mg g−1 ), and K is the Langmuir adsorption equi-
Such a fast adsorption rate could be attributed to the absence librium constant (L mg−1 ). As shown in the inset in Fig. 6,
of internal diffusion resistance, like the PAA-based magnetic the plot of Ce /q vs Ce at various temperatures yielded
nano-adsorbent developed in our previous work. straight lines, revealing that the adsorption of Cu(II) ions
The effect of pH on the adsorption of Cu(II) ions by on magnetic nano-adsorbent obeys the Langmuir adsorption
the magnetic nano-adsorbent at 300 K and the initial Cu(II) isotherm. From the slope and intercept, the values of qm and
ion concentrations of 200 and 1150 mg L−1 is illustrated in K might be estimated as 21.5 mg g−1 and 0.0165 L mg−1 ,
Fig. 5. It was found that the adsorption capacity increased respectively. It was notable that only 4.92 wt% of chitosan
with increasing the solution pH at an initial Cu(II) ion con- was responsible for the adsorption of Cu(II) ion. The max-
centration of 1150 mg L−1 . This might be due to the less imum adsorption capacity based on the weight of chitosan
insignificant competitive adsorption of hydrogen ions. At a was 437 mg g−1 , which was significantly higher than the
lower initial Cu(II) ion concentration (200 mg L−1 ), the ad- value 284 mg g−1 observed for the chitosan-coated silica
sorption capacity increased with increasing the solution pH beads by Shi et al. [37] and those values below 200 mg g−1
and then remained unchanged at pH 3–5. This might be due usually observed for the chitosan beads [30,38]. This might
to the fact that almost all Cu(II) ions were adsorbed. At be reasonably referred to the high specific surface area be-
450 Y.-C. Chang, D.-H. Chen / Journal of Colloid and Interface Science 283 (2005) 446–451

of Cu(II) ions from aqueous solutions at pH 2–5 due to


high specific surface area and the absence of internal diffu-
sion resistance. The time required to achieve the adsorption
equilibrium was only 1 min. Almost no Cu(II) ions were ad-
sorbed at pH 2, but the adsorption capacity was significantly
enhanced with the increase in pH. The adsorption behavior
followed the Langmuir adsorption isotherm with a maxi-
mum adsorption capacity of 21.5 mg g−1 and a Langmuir
adsorption equilibrium constant of 0.0165 L mg−1 at 300 K.
Also, the adsorption process was exothermic in nature with
an enthalpy change of −6.14 kJ mol−1 at 300–330 K. This
Fig. 7. Effect of temperature on the adsorption of Cu(II) ions by magnetic
nano-adsorbent. The inset is the plot of ln(q/Ce ) against 1/T .
work will be helpful for the development of adsorbents and
magnetic carriers.
cause the bound chitosan might be spread on the surface
of Fe3 O4 nanoparticles, leading to almost all chelation sites
available. Acknowledgment
The effect of temperature on the adsorption of Cu(II)
ions by the magnetic nano-adsorbent was investigated at This work was performed under the auspices of the Na-
pH 5, 300–330 K, and an initial Cu(II) ion concentration tional Science Council of the Republic of China, under
of 1100 mg L−1 . As shown in Fig. 7, the adsorption ca- Contract NSC 93-2214-E006-023, to which the authors ex-
pacity of Cu(II) ions decreased with increasing temperature. press their thanks.
The might be due to the fact that the electrostatic interac-
tion between Cu(II) ions and chitosan was lower at higher
temperatures. The plot of ln(q/Ce ) vs 1/T is shown in the References
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